CN114599605A - Method for forming carbonaceous structure and substrate having carbonaceous structure - Google Patents
Method for forming carbonaceous structure and substrate having carbonaceous structure Download PDFInfo
- Publication number
- CN114599605A CN114599605A CN202080074703.2A CN202080074703A CN114599605A CN 114599605 A CN114599605 A CN 114599605A CN 202080074703 A CN202080074703 A CN 202080074703A CN 114599605 A CN114599605 A CN 114599605A
- Authority
- CN
- China
- Prior art keywords
- dispersion
- carbonaceous
- substrate
- cnt
- dispersion medium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 180
- 238000000034 method Methods 0.000 title claims abstract description 91
- 239000006185 dispersion Substances 0.000 claims abstract description 177
- 239000012528 membrane Substances 0.000 claims abstract description 118
- 239000002612 dispersion medium Substances 0.000 claims abstract description 113
- 239000007788 liquid Substances 0.000 claims abstract description 108
- 239000011159 matrix material Substances 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 106
- 238000000967 suction filtration Methods 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 17
- 238000001704 evaporation Methods 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 description 165
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 132
- 239000011248 coating agent Substances 0.000 description 69
- 238000000576 coating method Methods 0.000 description 69
- 239000002041 carbon nanotube Substances 0.000 description 59
- 229910021393 carbon nanotube Inorganic materials 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 229910021389 graphene Inorganic materials 0.000 description 20
- 239000002109 single walled nanotube Substances 0.000 description 17
- 239000002585 base Substances 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000002238 carbon nanotube film Substances 0.000 description 7
- 230000002706 hydrostatic effect Effects 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 230000037303 wrinkles Effects 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000004931 aggregating effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910003472 fullerene Inorganic materials 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- -1 alkali metal salt Chemical class 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 229920003050 poly-cycloolefin Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XJGVBNMPIPKZCV-UHFFFAOYSA-N dimethyl(tridecyl)alumane Chemical compound CCCCCCCCCCCCC[Al](C)C XJGVBNMPIPKZCV-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1692—Other shaped material, e.g. perforated or porous sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/12—Special parameters characterising the filtering material
- B01D2239/1216—Pore size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
Abstract
The purpose of the present invention is to provide a novel method for forming a carbonaceous structure containing a fine carbonaceous body such as CNT. A method for forming a carbonaceous structure, in which a carbonaceous structure is formed on a surface of a base, comprising the steps of: a laminate forming step of forming a laminate in which a fine carbonaceous body dispersion liquid containing a fine carbonaceous body and a dispersion medium is filled in at least a part of a space between a porous film capable of holding the dispersion medium and a substrate; and a dispersion medium removing step of taking out at least a part of the dispersion medium to the outside of the laminate through the porous membrane and/or the matrix.
Description
Technical Field
The present invention relates to a method for forming a carbonaceous structure and a substrate having a carbonaceous structure.
Background
In various semiconductor devices including a display device and the like, a wiring layer for electrically connecting components such as a transistor, a capacitor, and a photoelectric converter constituting the device is necessary. Conventionally, the wiring layer has been formed mainly using a metal phase such as gold, silver, copper, or aluminum having high conductivity, but in recent years, attempts have been widely made to use sp of carbon atoms such as Carbon Nanotubes (CNTs) or graphene2The wiring layer of the device is formed of minute carbon bodies such as extremely minute carbon fibers or carbon particles formed by bonding.
In addition, taking advantage of the fact that the CNT has a very high field electron emission characteristic at the tip portion in particular, a CNT-containing film is expected to be used as an electrode for a field emission type cold cathode used in a fluorescent display tube, an X-ray tube, a Field Emission Display (FED), or the like. Further, by adjusting the shape of the above fine carbon body or the like, or by replacing a part of carbon atoms with other atoms, it is expected to use itself as a constituent element of a semiconductor.
When a wiring layer of a facility apparatus or the like is to be formed using a fine carbonaceous body, a step of forming a carbonaceous structure such as a carbonaceous film containing the fine carbonaceous body on the entire surface or a part of a predetermined substrate surface is necessary.
As a method for forming the carbonaceous structure on the surface of the substrate, a printing method in which a paste obtained by mixing a fine carbonaceous material such as CNT with a suitable binder or a dispersion obtained by dispersing a fine carbonaceous material such as CNT in a suitable dispersion medium is applied to the surface of the substrate, a method for forming a structure such as a carbonaceous film on a substrate, and the like have been studied. According to the printing method, it is considered that the process for forming the carbonaceous structure can be stabilized and the cost can be reduced.
On the other hand, since the wettability of a fine carbonaceous body such as a CNT is generally low in a solvent or the like, it is not always easy to form a dispersion containing a high concentration of the fine carbonaceous body, and it is difficult to simply use a printing method because of the inherent characteristics of the fine carbonaceous body such as a CNT which is difficult to leave when the fine carbonaceous body is anchored on various surfaces, and various methods for avoiding these problems have been studied.
For example, in order to avoid a problem that it is difficult to form a dispersion containing CNTs or the like mainly at a high concentration, a transfer method has been studied in which a CNT dispersion or the like at a low density is filtered using a filter, CNTs or the like are deposited on the surface of the filter, and the deposited CNTs or the like are transferred to the surface of a target substrate, thereby forming a desired carbonaceous film on the surface of the substrate.
For example, patent document 1 describes a method of depositing a carbonaceous anchor preparation mainly containing CNTs on a filter paper, and applying a load while overlapping the anchor preparation with a smooth metal surface and heating the mixture to transfer the mixture, thereby anchoring a carbonaceous aggregate to the metal surface, in order to use the mixture as a component of an FED, a capacitor, or the like. Patent document 2 also describes a method of transferring a CNT film to the substrate side by placing a filter, which filters a CNT dispersion and deposits CNTs, on a metal substrate for an electron source and applying pressure thereto. Non-patent document 1 describes a method in which a CNT film formed on a filter by filtering a CNT dispersion and dried is brought into contact with a substrate, and is pressed to adhere to the substrate, and then the filter anchored to the CNT film is dissolved in an organic solvent to remove the filter, thereby transferring the CNT film to the substrate.
In addition, a method of depositing CNTs by a chemical vapor deposition method (CVD method) or the like using a predetermined metal catalyst or the like as a base point by adhering the metal catalyst or the like to the surface of a substrate on which a carbonaceous film is to be formed without using a form such as a dispersion medium; in addition to a method of depositing electric particles such as CNTs synthesized in advance on a substrate by an electrostatic action or the like, patent document 3 describes a technique of forming a transparent conductive film by aggregating CNTs deposited in a vapor phase on a filter to form a structure and transferring the structure onto a substrate. Non-patent document 2 describes a technique of forming a CNT transparent conductive film on a substrate by collecting CNTs deposited in a vapor phase on a filter to form an anchor preparation, pressing the anchor preparation onto a smooth substrate, and then peeling off the filter.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2008-273785
Patent document 2: japanese patent laid-open publication No. 2011-009131
Patent document 3: japanese patent laid-open publication No. 2014-044839
Non-patent document
Non-patent document 1: science, 305, 1273(2004)
Non-patent document 2: nano Letters, 10, 4349(2010)
Disclosure of Invention
Technical problem to be solved by the invention
As described above, a method for forming a carbonaceous structure on a substrate using a fine carbonaceous body such as CNT has not been established mainly due to various characteristics of the fine carbonaceous body.
In particular, in various methods using a dispersion liquid in which a fine carbonaceous body or the like is dispersed in a volatile dispersion medium, it is difficult to disperse the fine carbonaceous body or the like in the dispersion medium with a high density, and there is a problem that selection of the dispersion medium is limited, and on the other hand, depending on the kind of the dispersion medium, wettability with the surface of the substrate on which the carbonaceous structure is to be formed cannot be secured, and a problem occurs in that a liquid film of the dispersion liquid cannot be uniformly formed at a predetermined position on the surface of the substrate.
Further, in the method of depositing CNTs or the like on a filter by a vapor phase method to form a preform and transferring the preform to a substrate to form a carbonaceous structure on the surface of the substrate, since the preform is generally low in density, a step of pressing the preform against the substrate at a predetermined pressure and compressing the preform to obtain a carbonaceous structure is necessary. Further, the method which does not involve a dispersion of a fine carbonaceous body such as CNT is not free from opportunities to remove a catalyst or the like attached to the fine carbonaceous body or to perform various modifications, and has a problem in a step of removing a filter having an anchor such as a carbonaceous structure well after transfer.
As described above, the problem of the technique of forming a carbonaceous structure by forming a low-density preform on the surface of a filter or the like in advance and transferring the preform is obvious when a wiring layer, that is, a so-called top-contact structure is formed on a substrate on which a predetermined semiconductor structure or the like is previously fabricated. That is, when this method is used, it is necessary to select an appropriate pressing method for a dispersion medium or a preform that does not damage the underlying semiconductor structure or the like, and there is a problem that the step of forming a carbonaceous structure becomes complicated.
Furthermore, in the case of forming a semiconductor device or the like including a carbonaceous structure such as a wiring, a transparent conductive film, an electrode, a semiconductor structure or the like using a fine carbonaceous body such as CNT, there are naturally various demands for the formed carbonaceous structure to exhibit desired characteristics, and there are various demands for the structure or the manufacturing process thereof corresponding to various semiconductor devices without damaging the already formed structure or the like when the carbonaceous structure is formed, and to ensure low cost or high productivity.
Further, according to the above-described needs, it is expected that a novel carbonaceous structure formation method different from the conventional method can be provided, which facilitates the formation of the conventional semiconductor device structure, and which enables the formation of a novel semiconductor device structure.
Accordingly, an object of the present invention is to provide a novel method for forming a carbonaceous structure, and a substrate having a carbonaceous structure formed by the method, for a method for forming a carbonaceous structure using a dispersion liquid containing a fine carbonaceous body such as CNT.
Means for solving the problems
In order to solve the above-described problems, the present invention provides a method for forming a carbonaceous structure in which a carbonaceous structure is formed on a surface of a base, the method comprising the steps of: a laminate forming step of forming a laminate in which a fine carbonaceous body dispersion liquid containing a fine carbonaceous body and a dispersion medium is filled in at least a part of a space between a porous film capable of holding the dispersion medium and a matrix; and a dispersion medium removing step of taking out at least a part of the dispersion medium to the outside of the laminate through the porous membrane and/or the matrix.
In the above method, the porous membrane is formed by laminating the porous membrane, which holds the fine carbon body dispersion liquid by suction filtration, on the matrix.
In the above method, the porous membrane is formed by immersing the porous membrane in a solvent, and then the porous membrane is stacked on a substrate.
In the above method, a method of forming a carbonaceous structure is provided, wherein the dispersion medium contained in the fine carbonaceous body dispersion liquid is replaced with another dispersion medium in the suction filtration step.
In the method, the dispersion medium removing step is performed by evaporating the dispersion medium through pores of the porous film.
In the above method, there is provided a method for forming a carbonaceous structure, further comprising a step of removing the porous film from the formed carbonaceous structure.
Further, there is provided a method for forming a carbonaceous structure, wherein the step of removing the porous film is performed by peeling the porous film from the carbonaceous structure.
The present invention also provides a substrate having a carbonaceous structure comprising a fine carbon body, wherein the carbonaceous structure is formed in a process of taking out at least a part of a dispersion medium out of a laminate body through a porous film and/or a matrix, the laminate body being formed by filling at least a part of a space between the porous film and the substrate, the space being capable of holding the dispersion medium, from a fine carbon body dispersion liquid comprising the fine carbon body and the dispersion medium.
Effects of the invention
According to the present invention, a carbonaceous structure can be formed simply and efficiently. Further, by forming a predetermined structure particularly in the lower portion, a carbonaceous structure can be favorably formed also on a surface having irregularities or a curved surface.
Drawings
Fig. 1A shows a PET substrate having a CNT coating film formed thereon using a CNT aqueous dispersion.
Fig. 1B shows a PET substrate on which a CNT coating film is formed using a CNT aqueous dispersion.
Fig. 2A is an SEM image of a CNT coating film formed using the CNT aqueous dispersion.
Fig. 2B is an SEM image of a CNT coating film formed using the CNT aqueous dispersion.
Fig. 2C is an SEM image of a cross section of a CNT coating film formed using the CNT aqueous dispersion.
Fig. 3 shows a PET substrate having a CNT coating film formed using a CNT toluene dispersion.
Fig. 4A shows a glass substrate on which a CNT coating film is formed using a CNT toluene dispersion.
Fig. 4B shows a glass substrate coated with a fluororesin (Cytop) on which a CNT coating film is formed using a CNT toluene dispersion.
Fig. 4C shows a polycycloolefin resin having a CNT coating film formed using a CNT toluene dispersion.
Fig. 4D shows a PTFE resin with a CNT coating film formed using a CNT toluene dispersion.
Fig. 4E shows a curved glass surface on which a CNT coating film is formed using a CNT toluene dispersion.
Fig. 4F shows the surface of the aluminum foil on which the CNT coating film was formed using the CNT toluene dispersion.
Fig. 4G shows a rubber glove (nitrile rubber) having a CNT coating film formed using a CNT toluene dispersion.
Fig. 5A shows a PET substrate on which a mixed coating of CNT and graphene is formed using a toluene dispersion of CNT and graphene.
Fig. 5B is an SEM image of a mixed coating film of CNT and graphene formed using a toluene dispersion of CNT and graphene.
Fig. 6 is a schematic diagram showing the state of the liquid droplets infiltrating into the porous membrane.
Detailed Description
The present invention is characterized in that a carbonaceous structure is formed using the above-described fine carbonaceous body, utilizing various behaviors observed when a liquid and a porous film coexist.
1. Use of the porous Membrane according to the invention
The porous film of the present invention forms a laminate with a substrate via a dispersion of a fine carbonaceous body or the like, and thus has a function of preventing the dispersion from forming droplets on the substrate surface or the like, distributing the dispersion on the substrate surface with a substantially uniform film thickness, and also has a function of confining the fine carbonaceous body or the like in the dispersion between the substrate and the porous film. Further, in the process in which the dispersion medium is discharged from between the matrix and the porous membrane through the pores of the porous membrane, the porous membrane functions as a pressure medium that compresses the dispersion medium isotropically by the atmospheric pressure.
As a means for forming a liquid film having a substantially uniform film thickness by supplying various liquids to the surface of a substrate, a spin coating method, a spray method, or the like is generally used. In the dispersion liquid used in the present invention in which the above fine carbonaceous material or the like is dispersed, it is also desirable to form a uniform liquid film on the surface of the substrate by spin coating or the like mainly by adjusting the dispersion medium or the like.
However, as schematically shown in fig. 6(a), when the wettability between the liquid and the substrate surface is low, the contact area with the substrate surface is reduced by the surface tension of the liquid, and the surface area of the liquid itself is minimized, so that the liquid forms droplets on the substrate surface, and as a result, it is difficult to form a uniform liquid film. This phenomenon becomes remarkable particularly when the liquid film to be formed is thin.
On the other hand, as schematically shown in fig. 6(b), when a liquid is dropped on a porous film having a wettability equal to or higher than a certain value, a phenomenon is generally observed in which the liquid permeates and fills pores in the porous film by a so-called capillary phenomenon, and a liquid film is generated on the surface of the porous film as if the liquids filled in the pores are connected, thereby forming "film-like liquid droplets" including the porous film as a whole. In this way, it is a commonly observed matter that the liquid penetrates into the porous membrane, the form of the liquid changes, and a liquid film having a substantially uniform thickness is formed on the surface of the porous membrane and stably exists. In the present specification, the form of a liquid that stably spreads in a thin film form and thus includes the whole or a part of the porous membrane is sometimes referred to as "liquid droplets that wet the porous membrane".
Furthermore, for example, in the case of a substrate surface of a fluororesin or the like having high hydrophobicity, when it is a liquid such as water alone, it tends to be repelled from the surface to form droplets (fig. 6(a)), and when a porous film having a sufficient amount of liquid impregnated therein and formed as the above-described "droplets wet on the porous film" is provided on the surface, the porous film or the like adheres to the substrate surface via the liquid and adheres stably, which is also a phenomenon that is generally observed (fig. 6 (c)). In this case, it was observed that the thickness of the liquid film present between the porous film and the substrate surface was substantially uniform regardless of the shape of the substrate surface and the like.
The present invention utilizes the above-described phenomenon observed in a liquid that wets a porous membrane, and prevents a dispersion liquid containing a dispersion medium having low wettability with a substrate from being converted into droplets on the surface of the substrate, and forms desired carbonaceous structures on the surface of the substrate, even when a dispersion medium having low wettability with the substrate is used.
That is, one aspect of the present invention is characterized in that a porous film is laminated on a surface of a substrate on which a carbonaceous structure is to be formed via a dispersion liquid in which a fine carbonaceous body or the like constituting the carbonaceous structure is dispersed, thereby forming a laminate, the porous film is adhered to the substrate by surface tension of the dispersion liquid, and a liquid film of the dispersion liquid is held on the surface of the substrate with a substantially uniform thickness regardless of whether the wettability of the dispersion liquid with the substrate is good or not.
In this case, since the soft porous film is used, even when the surface of the substrate has irregularities or the surface of the substrate is curved, the porous film is autonomously deformed by the surface tension of the dispersion and is thus brought into close contact with the substrate, whereby the liquid film of the dispersion can be held on the surface of the substrate with a substantially uniform thickness as in the case of a flat substrate. Further, since the porous membrane is sufficiently wetted with the dispersion liquid, fine wrinkles, shrinkage, and the like of the porous membrane are autonomously eliminated as compared with the case of the dry state, and therefore, it is also effective in preventing unevenness, positional displacement, and the like of the formed carbonaceous structure.
Further, it is also effective in that a porous film having a pore diameter of such a size that the fine carbonaceous body or the like as a dispersoid in the dispersion cannot substantially pass therethrough is used to substantially seal the fine carbonaceous body or the like between the substrate and the porous film, thereby facilitating the formation of the carbonaceous structure thereafter.
In another aspect of the present invention, in a laminate in which a substrate and a porous film are laminated via a dispersion liquid in which the fine carbonaceous body and the like are dispersed, for example, by gradually evaporating a dispersion medium contained in the dispersion liquid from the back surface side of the porous film, the dispersion medium present between the substrate and the porous film is sucked out through pores of the porous film, and as a result, the distance between the substrate and the porous film is reduced. In this process, the fine carbonaceous bodies and the like, which are dispersoids present between the substrate and the porous film, are compressed and aggregated between the substrate and the porous film, and as a result, carbonaceous structures can be formed.
The force of compressing the fine carbonaceous body or the like between the substrate and the porous film is such that atmospheric pressure acts as isotropic hydrostatic pressure via the soft porous film, and acts uniformly regardless of the surface shape of the substrate, and is effective in that, particularly, when the upper electrode in the top-contact structure is formed, the structure or the like previously formed on the surface of the substrate is not broken.
2. The method for forming a carbonaceous structure of the present invention
(1) The fine carbon bodies used in the present invention
As the fine carbonaceous body used for forming the carbonaceous structure in the present invention, a fine carbonaceous body such as CNT, graphene, fullerene, or the like, which is obtained by an industrial method, is preferably used. The CNTs have a specific chemical and physical characteristics, which are based on a hexagonal lattice structure formed of carbon atoms, and have a specific secondary structure by combining a single layer or a plurality of layers of the structure. In particular, a carbonaceous structure having a characteristic can be formed by utilizing the extremely high conductivity of CNT or graphene or the property as a semiconductor exhibited by a part of CNT or fullerene. On the other hand, since the above-mentioned fine carbonaceous bodies such as CNTs have an extremely high specific surface area, etc., there are various difficulties in forming a carbonaceous structure by a method of a printing method.
In the present invention, a solvent having a volatility which can be easily removed is used as a dispersion medium, a dispersion liquid in which the above-described fine carbomorphites and the like are dispersed is prepared in advance, and the dispersion liquid is treated in a state in which the surfaces of the various fine carbomorphites are covered with the dispersion medium, whereby the carbonaceous structure is formed by a printing method in a solution process while suppressing the expression of various characteristics exhibited by the fine carbomorphites between the fine carbomorphites or firmly anchored to a porous film or the like which is in contact with the fine carbomorphites.
(2) About dispersion liquid
According to the present invention, in the step of forming a carbonaceous structure on a substrate, first, a dispersion liquid in which a fine carbonaceous body or the like capable of forming a carbonaceous structure is dispersed in an appropriate dispersion medium is prepared. In the present invention, the dispersion may be in a state in which the surface of the dispersoid is covered with the dispersion medium by immersing the dispersoid in the dispersion medium, and the dispersoid is aggregated within this range, between the dispersoids, or between the dispersoid and the porous membrane, so that redispersion can be easily performed. That is, the dispersion liquid in the present invention may be any dispersion liquid as long as it is substantially uniformly present in a predetermined time period after being homogenized by ultrasonic waves, stirring treatment or the like, and the fine carbonaceous bodies or the like as a dispersoid in the dispersion medium are stably dispersed without substantial interaction of the dispersoid in the dispersion medium, and may be a dispersion liquid in which the dispersoid is precipitated when left to stand for a long time after stirring the dispersion medium, or a dispersion liquid in which the dispersoid is precipitated in a state in which the dispersoid can be easily redispersed in the dispersion medium. By being held in this dispersion liquid, the surface of the fine carbonaceous body or the like is covered with the dispersion medium, and thus strong anchoring or the like between the fine carbonaceous bodies or between the porous film or the surface of the substrate and the fine carbonaceous body is less likely to occur.
In the present invention, the structure and the like of the fine carbonaceous bodies used for forming the carbonaceous structures are not particularly limited, and may be appropriately determined depending on the intended carbonaceous structures within a range where the fine carbonaceous bodies are present in the dispersion medium substantially uniformly for a predetermined time by ultrasonic waves, stirring treatment, or the like. Examples of the fine carbon bodies include Carbon Nanotubes (CNTs), graphene, and fullerene.
The fine carbonaceous material can be used by dispersing it in a dispersion medium by using an auxiliary agent or the like having a surface-active action of improving the affinity with the dispersion medium and facilitating dispersion, if necessary. For example, when the CNT is used as a fine carbon body, a surfactant having a known surface-active effect, such as sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, dodecyltrimethylaluminum bromide, TritonX-100, or polyvinylpyrrolidone, can be used. In addition, by using a carbon-based compound having an aromatic ring or the like such as cresol, CNTs can be dispersed in a suitable dispersion medium at a high concentration. Further, by using an acidic liquid such as chlorosulfonic acid, CNTs can be dispersed at a high concentration. Further, an alkali metal salt or an aluminum salt may be used as a dispersion aid to improve the dispersibility of CNTs in alcohols and the like.
The fine carbonaceous body used in the present invention is not necessarily composed of high-purity carbon, and may contain various additives or impurities depending on the intended carbonaceous structure. In addition, in the dispersion liquid used in the present invention, components other than the fine carbonaceous bodies may be mixed according to the target carbonaceous structure.
The density of the fine carbonaceous body in the dispersion liquid used in the present invention may be suitably determined depending on the kind of the fine carbonaceous body or dispersion medium used, the structure of the carbonaceous structure to be formed, the specific means for forming the carbonaceous structure, and the like, and may be, for example, 5, 0.1, 0.01, 0.001 wt%. When a porous membrane such as a membrane filter is used and fine carbonaceous bodies are concentrated on the porous membrane by means such as suction filtration, a dispersion containing fine carbonaceous bodies at a thinner density can be used.
The dispersion medium constituting the dispersion liquid used in the present invention is not particularly limited, and may be a solvent such as toluene, chlorobenzene, ethanol, 2-methoxyethanol, ethylene glycol, acetone, methyl ethyl ketone, ethyl acetate, hexane, octane, terpineol, γ -butyrolactone, chloroform, DMF, DMSO, THF, or water as a main component, and may be appropriately determined in consideration of the requirements (wettability with the substrate, corrosiveness to the substrate, and the like) of the surfactant used or the substrate, volatility at the time of removing the solvent, and the like.
Further, in order to meet the demand of the matrix to be formed into the carbonaceous structure, for example, a dispersion liquid of the fine carbonaceous body or the like is filtered on the porous membrane to enrich the fine carbonaceous body or the like, the dispersion medium is removed by a method such as suction, and at the same time, another dispersion medium or the like is supplied to replace the dispersion medium, and then the dispersion medium is superposed on the matrix to form a laminate.
(3) Porous membrane for use in the present invention
The porous membrane used in the present invention may be suitably used as long as it has pores communicating between the front surface and the back surface in the interior thereof and can hold the dispersion medium in the dispersion liquid. In particular, it is preferable to use a porous film which shows good wettability to an appropriate solvent when immersed in the solvent and is flexible, and therefore can be easily adhered to a substrate having various irregularities in a wet state without a void when the substrate is attached.
As schematically shown in fig. 6(b), when a porous membrane having fine interconnected pores is immersed in a solvent or the like to wet the porous membrane, a liquid penetrates and fills the pores in the porous membrane by a so-called capillary phenomenon, and a liquid film is generated on the surface of the porous membrane so as to connect the liquids filled in the pores, thereby generating a membrane-like "liquid droplet wetted with the porous membrane" including the porous membrane as a whole.
In the present invention, the porous membrane capable of retaining the dispersion medium means that the liquid forming the "liquid droplets wetting the porous membrane" does not separate from the porous membrane only by the action of gravity because the diameter of the communicating pores contained in the porous membrane is sufficiently small. In the present invention, by forming a laminate in which a porous membrane capable of holding the dispersion medium and a matrix are laminated through the dispersion liquid, particularly in the process of removing the dispersion medium from the surface of the porous membrane by evaporation or the like, the space between the porous membrane and the matrix is reduced by the atmospheric pressure, and the compression of the fine carbonaceous body as the dispersoid can be generated.
On the upper surface of the porous film on which the "liquid droplets wetting the porous film" are formed, a liquid phase having a thickness mainly corresponding to the pore diameter of the porous film can be held by the surface tension of the liquid droplets (dispersion medium). On the other hand, for example, as performed in suction filtration, the liquid phase can be removed by suction through the communicating pores of the porous membrane by providing a pressure difference between the front and back surfaces of the porous membrane or bringing dry filter paper or the like into contact with the porous membrane.
Further, by using a porous membrane having a pore diameter such that the dispersoid in the dispersion liquid cannot pass therethrough, the porous membrane capable of holding the dispersion medium can mainly hold the dispersoid contained in the dispersion liquid on the upper surface side of the porous membrane (the surface to which the dispersion liquid is supplied). In this state, the porous membrane can be regarded as a container that holds the dispersion liquid on its upper side (the side to which the dispersion liquid is supplied) mainly by the surface tension of the dispersion medium or the like.
As the porous membrane capable of holding the dispersion medium, a porous membrane generally used as a filter in filtration can be preferably used. In particular, it is preferable from the viewpoint that the fine carbonaceous body can be held only on the surface side of the porous membrane by using a filter which is different from a normal filter paper formed by reinforcing various fibers and which is generally called a membrane filter and which can mainly hold a filter on the surface of the filter.
As a membrane filter to be preferably used, a membrane filter mainly composed of PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), cellulose mixed ester, cellulose acetate, polycarbonate, or the like and having a pore diameter of 8 or less, 0.5 or less, 0.1 or less, 0.025 or less, or the like can be suitably used depending on a solvent or the like used as a dispersion medium.
(4) Formation of a laminate comprising a porous Membrane/Dispersion/matrix
When a dispersion containing a fine carbonaceous body at a high density is used, the fine carbonaceous body can be supplied to the porous membrane at a density sufficient to form the carbonaceous structure by appropriate means such as dropping the dispersion on the porous membrane, performing spin coating, spraying, or the like, or immersing the porous membrane in the dispersion, and a laminate of the matrix and the porous membrane can be formed by superposing the matrix on the surface of the porous membrane holding the dispersion, with the dispersion interposed therebetween. Alternatively, when the dispersion is dropped on the surface of the substrate, the porous film is superposed on the surface of the substrate, and a laminate of the substrate and the porous film is formed through the dispersion. At this time, as the porous film laminated on the surface of the base to which the dispersion liquid is dropped, it is effective to use a porous film into which an appropriate solvent is previously permeated in order to form a good laminated body which prevents the shortage of the dispersion liquid between the base and the porous film.
On the other hand, when a dispersion containing a fine carbonaceous body or the like at a low density is used, a porous membrane is used as a filtration membrane, and after a desired amount of the fine carbonaceous body or the like is concentrated on the porous membrane by subjecting the dispersion to suction filtration or the like, a substrate is superposed on the side (mainly the upper surface) of the porous membrane on which the fine carbonaceous body or the like is present, and a laminate of the substrate and the porous membrane is formed via the dispersion.
As means for enriching the fine carbonaceous body and the like on the porous membrane, in addition to suction filtration by providing a pressure difference on the porous membrane, an appropriate means such as a method of stacking a filter paper or the like on the back surface of the porous membrane and removing the dispersion medium in the dispersion liquid by the surface tension of the dispersion medium, and evaporating the dispersion medium at a predetermined ratio from the porous membrane supplied with the dispersion liquid can be used.
As described above, when a desired amount of fine carbonaceous bodies or the like is concentrated on the porous membrane by suction filtration or the like using a dispersion containing the fine carbonaceous bodies or the like at a low density, the fine carbonaceous bodies or the like can be concentrated on the porous membrane at a uniform density. Further, it is also preferable that the CNT is subjected to a process such as suction filtration to cause aggregation due to entanglement of fibers, for example, whereby the fine carbon bodies and the like are uniformly weakly adsorbed on the surface of the porous membrane, and the aggregated fine carbon bodies and the like are prevented from running off in a subsequent step. Further, depending on the structure of the formed carbonaceous structure, carbonaceous structures having various laminated structures can be formed by using a plurality of types of dispersion liquids in sequence.
When the fine carbonaceous bodies and the like in the dispersion liquid are dried by excessive removal of the dispersion medium, the fine carbonaceous bodies and the like adhere to the porous film, and the carbonaceous structures are difficult to form on the surface of the substrate thereafter. Therefore, in order to maintain the fine carbonaceous bodies and the like in a wet state, the suction filtration of the dispersion is preferably completed with an appropriate amount of the dispersion medium remaining.
In addition, when it is necessary to replace the dispersion medium with a dispersion medium different from the dispersion medium contained in the dispersion liquid, to remove impurities adhering to the fine carbon bodies and the like, it is effective to add an appropriate solvent to the dispersion liquid side in the above-mentioned suction filtration process. In this case, since the fine carbonaceous bodies and the like can be uniformly and weakly adsorbed on the surface of the porous membrane by suction filtration of the dispersion as described above, a solvent having low dispersibility of the fine carbonaceous bodies used by substitution after suction filtration can be used.
As described above, it is preferable from the viewpoint that the porous membrane enriched with the fine carbonaceous body or the like by suction filtration or the like of the dispersion liquid is immersed in an appropriate solvent thereafter, or the solvent is supplied by a spraying method to include a sufficient amount of the dispersion medium in the porous membrane, whereby wrinkles or shrinkages occurring in the porous membrane can be eliminated, and moreover, a lubricating effect is also generated at the time of lamination with the substrate, and therefore, good lamination is easily performed.
Further, by superposing the base on the surface of the porous membrane holding the dispersion (or superposing the porous membrane on the surface of the base holding the dispersion), the dispersion medium is expanded while excluding the gas phase between the porous membrane and the base by the so-called capillary phenomenon, the space between the porous membrane and the base is filled, and a laminate composed of the porous membrane/the liquid phase (dispersion)/the base is formed via the liquid phase having a thickness determined by the kind of the dispersion medium and the like. In this laminate, since the porous membrane is flexible, an isotropic hydrostatic pressure having a magnitude comparable to the atmospheric pressure is generated in the dispersion liquid between the porous membrane and the matrix.
In the above-mentioned overlapping step, it is effective that the dispersion liquid can be satisfactorily filled in the porous membrane and the matrix by, for example, pressing the porous membrane against the matrix side within a range where the liquid membrane of the dispersion liquid is not cut, without leaving an unintentional gas phase (bubble) between the porous membrane and the matrix, or without forming wrinkles in the porous membrane.
In the laminate in which the porous film and the matrix are stacked via the dispersion liquid, it is preferable that at least a part of the space between the porous film and the matrix is filled with the dispersion medium (liquid phase) and the dispersion medium such as the fine carbonaceous body is impregnated in the dispersion medium, in order to compress and aggregate the fine carbonaceous body and the like in the removal process of the dispersion medium to form the carbonaceous structure as described below.
For example, when a thin film-like carbonaceous structure such as a transparent conductive film is formed using a fine carbonaceous body or the like, the amount per unit area of the fine carbonaceous body or the like is small, and therefore, in general, the fine carbonaceous body or the like can be held in a liquid film formed by the surface tension of a solvent and stacked in this state, and a preferable laminate can be formed.
On the other hand, when the amount of fine carbon bodies or the like per unit area is large for forming a discharge electrode or the like composed of CNTs or the like, it is preferable to form a laminate while maintaining an amount of dispersion medium that can sufficiently impregnate the fine carbon bodies or the like by appropriately using a means for preventing outflow of the dispersion liquid (dispersion medium).
In the laminate, the dispersion liquid containing the fine carbonaceous bodies or the like is in contact with the entire surface of the substrate, whereby a uniform carbonaceous structure can be formed on the entire surface of the substrate.
On the other hand, when forming a carbonaceous structure on a part of the surface of the substrate, the carbonaceous structure can be formed on a predetermined position of the surface of the substrate by, for example, forming a mask layer using a resist or the like on the surface of the substrate in advance to restrict the position where the dispersion comes into contact with, or making the fine carbonaceous body or the like easily bonded (or difficult to bond) to a predetermined position of the surface of the substrate by various surface modifications.
Alternatively, the carbonaceous structures can be formed at predetermined positions on the surface of the substrate even when the porous membrane is laminated with the substrate in a state where the pattern of the fine carbonaceous bodies or the like is formed on the surface of the porous membrane by performing a treatment of closing pores in a predetermined region of the porous membrane, then performing suction filtration of the dispersion, or performing predetermined drawing on the porous membrane using the dispersion.
In the laminate in which the porous film and the substrate are laminated via the dispersion liquid, the dispersion liquid may fill the entire area between the porous film and the substrate, or may partially fill the positions where the carbonaceous structures are formed.
In the laminate in which the porous film and the matrix are stacked via the dispersion, the dispersion layer may generally have a thickness of about 1 to 1000 μm. The thickness of the dispersion layer is a sufficiently large space compared with the fine carbonaceous body and the like used in the present invention, and the dispersoid performs the same behavior in the dispersion medium. Further, by using the dispersion liquid layer as a reaction vessel and making a substance which causes a predetermined reaction with the fine carbonaceous body or the like exist in the dispersion liquid, various functions and the like can be imparted to the carbon structure formed later.
(5) Concerning removal of the dispersion medium from the laminate, etc
In the laminate composed of the porous membrane/dispersion/matrix formed as described above, the distance between the porous membrane and the matrix is reduced by removing the dispersion medium mainly from the surface on the outer side of the porous membrane, and in this process, the fine carbonaceous bodies and the like in the dispersion are compressed by the isotropic hydrostatic pressure, and the carbonaceous structures are formed.
The dispersion medium can be removed from the laminate by, for example, allowing the porous membrane of the laminate to stand upward, or evaporating the dispersion medium from the outer surface of the porous membrane. In this case, the rate of removal of the solvent from the laminate can be increased by heating the laminate to an appropriate temperature equal to or lower than the boiling point of the dispersion medium. Further, the solvent may be removed from the laminate by bringing an absorbent such as filter paper, which absorbs the solvent, into contact with the surface of the porous membrane of the laminate or by applying a negative pressure. At this time, the laminate may be pressed from the outside as necessary.
The removal of the dispersion medium from the laminate is not particularly limited as long as it is carried out through the porous membrane, and for example, it may be carried out from the substrate side by providing a gas-permeable hole on the substrate side, or by allowing the dispersion medium to be absorbed into the substrate.
In the step of removing the dispersion medium, first, the volume of the liquid film existing on the outer side of the porous film is reduced. Further, the liquid film present on the surface of the porous film generates a force to maintain the film thickness at a constant value or more due to the requirement of the surface tension, and therefore, the dispersion medium present in the interconnected pores in the porous film is sucked, and as a result, the dispersion medium present between the porous film and the substrate moves to the outer surface of the porous film, and the distance between the porous film and the substrate is reduced by the isotropic hydrostatic pressure.
It is considered that the distance reduction between the porous membrane and the matrix in the above mechanism continues until the liquid film between the porous membrane and the matrix is broken due to the decrease in the total volume of the dispersion medium, and as a result, in this process, the dispersoid present between the porous membrane and the matrix is in sandwiched contact with the porous membrane and the matrix, and then is anchored on the surface of the porous membrane or the matrix by intermolecular force or the like.
After evaporation of the liquid phase (dispersion medium) from the surface of the porous film or the like is sufficiently performed or after evaporation is substantially completed, the porous film is removed from the substrate by an appropriate means as necessary, and a matrix in which the carbonaceous structures are anchored on the surface is obtained as a dispersion of fine carbon particles or the like. The most simple way to remove the porous film is to peel off and remove the porous film from the surface of the carbonaceous structure formed as described above. On the other hand, the porous film is dissolved and removed with an appropriate solvent or the like, whereby damage or the like to the formed carbonaceous structure can be prevented.
It is considered that the surface of the porous film/substrate in contact with the carbonaceous structure formed by compressing the above fine carbonaceous body or the like by isotropic hydrostatic pressure is anchored to the carbonaceous structure by a predetermined intermolecular force or the like corresponding to the material or the like of the porous film/substrate. On the other hand, in the porous film, since the effective area in contact with the carbonaceous structures is small due to the porous structure, the adhesive force to the carbonaceous structures is small, and as a result, a large proportion of fine carbonaceous bodies and the like are anchored as carbonaceous structures on the surface of the substrate even when the porous film is peeled. Further, by adjusting the material or surface of the porous film or the matrix in consideration of the affinity with the dispersoid, the dispersoid can be effectively anchored as a carbonaceous structure on the side of the matrix surface.
As described above, in the method of bonding the dispersion medium constituting the dispersion liquid existing between the porous membrane and the matrix by aggregating the dispersoids existing in the dispersion medium by the isotropic hydrostatic pressure due to the surface tension or the like, for example, the following advantages are provided as compared with the method of transferring the fine carbon matrix or the like deposited on the filter paper or the like by pressing the matrix.
Since the fine carbonaceous body or the like is treated as a dispersion in a dispersion liquid in a state that the surface is covered with a dispersion medium, it is possible to anchor and form a carbonaceous structure uniformly on the surface of the substrate while avoiding the occurrence of undesirable anchoring or the like even for a substance which has a strong interaction with another substance and is likely to be anchored.
Further, by using a porous film having a predetermined flexibility, since the dispersoids can be anchored over the entire surface of the substrate under the same pressure condition, the carbonaceous structures can be formed with high uniformity even for a substrate having a large area. In particular, when the surface of the substrate has irregularities or the substrate has a curved surface, the fine carbonaceous bodies and the like may be anchored in a uniform pressure state to form the carbonaceous structure. In the method of compressing the fine carbonaceous body or the like by isotropic hydrostatic pressure between the porous film and the matrix which are sufficiently wetted with the dispersion, the deviation between the porous film and the matrix is less likely to occur while the wrinkles, shrinkages, or the like of the porous film are autonomously eliminated, and therefore a satisfactory carbonaceous structure can be formed.
Furthermore, for example, in the manufacturing process of various semiconductor devices, when wiring using a fine carbon body or the like is formed on the surface of various structures already formed on the lower part by a so-called top contact type structure, if a dispersion medium that does not affect the lower part structure by dissolution or the like is selected, the carbonaceous structure can be formed without substantial pressurization, and thus, breakage or the like of the lower part structure can be prevented.
Examples
The method of the present invention will be described in more detail below with reference to examples. The following examples are one embodiment of the present invention, and the present invention is not limited to these examples.
Example 1
A CNT coating film as an example of a carbonaceous structure was formed on a PET substrate as follows. As the minute carbonaceous body, single-walled Carbon nanotubes (edps INK (EC-DH), manufactured by famous Nano Carbon) dispersed in water were used.
0.5mL of distilled water was added to 1.0mL of the aqueous CNT dispersion to adjust the concentration, and a PTFE membrane filter (Millipore JGWP02500, 25 mm. phi., pore size 0.2 μm) as a porous membrane was impregnated with the aqueous CNT dispersion sufficiently. Next, the filter impregnated with the aqueous CNT dispersion was taken out of the aqueous CNT dispersion and quickly attached to the dried PET substrate. The filter attached to the PET substrate was in contact with the surface of the PET substrate through the CNT aqueous dispersion on the entire surface.
Thereafter, the PET substrate was placed on a hot plate, heated and maintained at 90 ℃ to evaporate water from the CNT aqueous dispersion. As the water evaporates off, the filter changes from a translucent state to a gray opaque state. In addition, in the process of attaching the filter to the PET substrate and evaporating and removing water, an operation of pressing the filter or the like is not particularly performed. After the water was evaporated and removed, the filter was peeled off from the PET substrate, and a black/translucent coating film having the same shape as the filter was observed on the surface of the PET substrate.
Fig. 1A shows a photograph of a black/translucent coating film observed on the surface of the PET substrate. The transmission spectrum (Shimadzu UV-2700, visible light region 380nm to 750nm) of the PET substrate having the black/translucent coating film adhered thereto was measured, and the average transmittance was 51.6%. Further, the surface resistance was measured (K-705 RS, Co., Ltd.), and it was found to be 60.8. omega./□, showing high conductivity.
From the above-mentioned measurement results of the surface resistance and the like, it is considered that the black/translucent coating observed on the surface of the PET substrate after the filter was peeled off is a CNT thin film in which CNTs in the CNT aqueous dispersion adhered to the filter are aggregated and adhered to the surface of the PET substrate.
The mechanism of forming the CNT thin film on the PET substrate surface by the above-described process is considered as follows. That is, by evaporating and removing the dispersion medium (water) through the filter surface in a state where the filter is laminated on the PET substrate surface through the CNT water dispersion liquid, the distance between the filter and the PET substrate is reduced, the CNTs are compressed and dried between the filter and the base material, and the CNTs are aggregated and adhered to the PET substrate surface by direct contact between the CNTs without the dispersion medium or direct contact between the CNTs and the PET substrate surface.
Example 2
A CNT coating film, which is an example of a carbonaceous structure, was formed by a transfer method using a CNT aqueous dispersion (edps INK (EC-DH) manufactured by famous Nano Carbon).
1.0mL of the CNT aqueous dispersion was diluted with 9.0mL of distilled water, and 20. mu.L of the diluted solution was further diluted with 5.0mL of distilled water to obtain a concentration-adjusted CNT aqueous dispersion. The CNT aqueous dispersion was suction filtered using a PTFE membrane filter (Millipore JGWP02500, 25 mm. phi., pore size 0.2 μm) until the dispersion on the filter disappeared immediately, thereby enriching the CNT on the filter. Next, the step of supplying an appropriate amount of distilled water to the filter and performing suction filtration was repeated 3 times to wash and remove the dispersant (surfactant) attached to the CNTs, and finally the suction filtration was terminated until the dispersion on the filter disappeared immediately.
Thereafter, the filter was taken out of the suction filter and immersed in a water bath, whereby the filter absorbed sufficient water, and after wrinkles or shrinkages were eliminated, the filter was quickly attached to the dried PET substrate. The filter attached to the PET substrate was in close contact with the surface of the PET substrate through the CNT aqueous dispersion on the entire surface. Thereafter, water was evaporated off on a hot plate maintained at 90 ℃ in the same manner as in example 1, and then the membrane filter was peeled off to form a black/translucent coating film on the surface of the PET substrate.
Fig. 1B shows a photograph of the black/translucent film formed as described above. The diluted CNT dispersion was used to enrich CNTs on the filter by suction filtration, thereby obtaining a coating film with higher uniformity than in example 1. The average transmittance of the PET substrate having the film attached thereon was measured in the same manner as described above and was 80.8%. The surface resistance was 233 Ω/□, and it is considered that the CNT film was formed by aggregating CNTs and adhered to the surface of the PET substrate.
In addition, in the process of forming the CNT coating film according to the above-described example, when the step of collecting CNTs on the membrane filter by suction filtration of the CNT aqueous dispersion is performed, CNTs in the dispersion are weakly adsorbed on the surface of the filter by some mechanism. This was confirmed by the fact that the CNTs remained substantially on the filter surface when the filter enriched with the CNTs was immersed in a water bath.
On the other hand, the filter in which the CNTs were enriched was used, and the CNT coating film was formed on the surface of the PET substrate in the same manner as in example 1, and it is considered that the adsorption of the CNTs on the surface of the filter by the suction filtration was caused by a weak force, and in the subsequent process, the CNTs easily adhered to the surface of the PET substrate to form the CNT coating film.
Example 3
As the fine carbonaceous body, a CNT coating film, which is an example of a carbonaceous structure, was formed using a single-walled carbon nanotube (SWCNT) produced by an ultrarapid growth method (ZEON ZEONANO SG 101).
To 5.0mL of distilled water in which 50mg of sodium dodecyl sulfate (kanto chemical specialty) as a surfactant for dispersing CNTs in water was dissolved, 0.50mg of the above single-walled carbon nanotube (ZEON ZEONANO SG101) was added, and ultrasonic treatment was performed for 1 hour using an ultrasonic homogenizer (bran son silicon r 250), thereby obtaining a CNT aqueous dispersion.
A CNT coating film was formed on a PET substrate in the same manner as in example 2, except that 60 μ L of the CNT aqueous dispersion was diluted with 5.0mL of distilled water. The average transmittance of the PET substrate to which the CNT coating film was attached was 79.1% and the surface resistance thereof was 2.56k Ω/□, which were measured in the same manner as described above.
Example 4
A CNT coating, which is an example of a carbonaceous structure, is formed using single-walled carbon nanotubes (SWCNTs) produced by the eDIPS method (manufactured by OSAKA SODA corporation, carbon purity > 99%, center diameter 1-3 nm) as a fine carbonaceous body.
0.50mg of the single-walled carbon nanotube (manufactured by OSAKA SODA) was added to 5.0mL of distilled water containing 500mg of sodium dodecyl sulfate as a surfactant, and ultrasonic treatment was performed for 1 hour using an ultrasonic homogenizer to obtain an aqueous CNT dispersion, 80. mu.L of the aqueous CNT dispersion was diluted with 5.0mL of distilled water to obtain an aqueous CNT dispersion, and a CNT coating was formed on a PET substrate in the same manner as in example 2 except that this aqueous CNT dispersion was used. The average transmittance of the PET substrate having the CNT coating film attached thereon, which was measured in the same manner as described above, was 74.5%, and the surface resistance was 270 Ω/□.
The results of examples 1 to 4 show that when CNTs having different properties produced by different production methods are used, a CNT coating film can be formed on a substrate by the present invention.
Example 5
The fine structure of the CNT coating films formed in examples 3 and 4 was confirmed as follows.
Dispersions were prepared in the same manner as in examples 3 and 4, and a CNT coating film was formed on a glass substrate by suction filtration on a filter or the like. The formed CNT coating was observed by a scanning electron microscope (Japanese Electron JSM-7600F).
Fig. 2A shows an SEM image of a coating film formed of CNTs manufactured by the ultrarapid growth method (example 3), and fig. 2B shows an SEM image of a coating film formed of CNTs manufactured by the edps method (example 4). In any of the CNT films, it was confirmed that the CNTs in a fiber form were entangled with each other and anchored on the surface of the substrate.
Fig. 2C shows an SEM image of a cross section of the glass substrate on which the CNT coating film shown in fig. 2B is formed. It was confirmed that the thickness of the CNT coating film formed on the substrate in example 4 was about 50 nm.
Example 6
A single-walled carbon nanotube (SWCNT) produced by an ultrarapid growth method (ZEON zeonono SG101) was used as a fine carbonaceous body, and a CNT coating film, which is an example of a carbonaceous structure, was formed using toluene as a dispersion medium for dispersing the CNTs.
To prepare CNTs dispersible in toluene, 0.50mg of the single-walled carbon nanotube (ZEON ZEONANO SG101) was added to 5.0mL of m-cresol (tokyo chemical corporation, > 98.0%) and the CNTs were dispersed in the m-cresol by ultrasonic treatment for 2 hours using an ultrasonic homogenizer (brasson silicon 250). The CNT dispersion was centrifuged (15000g, 1 hour) using a microfuge centrifuge (KUBOTA 3780), and the black supernatant was separated from the precipitate.
mu.L of the centrifuged supernatant was diluted with 5mL of toluene (Kanto chemical special grade) to prepare a CNT toluene dispersion. In the CNT-toluene dispersion, it was observed that CNTs as a dispersoid were uniformly dispersed in toluene.
Subsequently, the prepared CNT toluene dispersion was suction-filtered using a PTFE membrane filter (Millipore JGWP02500, 25 mm. phi., pore size 0.2 μm), and the CNTs were collected on the filter. Suction filtration was carried out until the dispersion on the filter disappeared immediately.
Thereafter, the filter was taken out of the suction filter and immersed in a toluene bath so that the filter absorbed sufficient toluene, and then was rapidly attached to the dried PET substrate. The filter attached to the PET substrate was in contact with the surface of the PET substrate through the CNT-toluene dispersion over the entire surface. Thereafter, a black/translucent CNT coating film was formed on the surface of the PET substrate by peeling off the filter after evaporating toluene on a hot plate maintained at 70 ℃ in the same manner as in example 1.
Fig. 3 shows a photograph of the black/translucent CNT coating film formed as described above. When toluene was used as the dispersion medium, a CNT coating film was formed in the same manner as in examples 1 to 5 using an aqueous dispersion. The average transmittance of the PET substrate having the film attached thereon was measured in the same manner as described above and was 78.1%. The surface resistance was 2.96 k.OMEGA./□.
In addition, as in the case of the CNT aqueous dispersion (example 2 and the like), as described above, it was observed that CNTs substantially remained on the filter surface even when the filter after suction filtration of the CNT toluene dispersion was immersed in a toluene bath. On the other hand, it was observed that the CNTs were completely removed from the filter within several seconds by subjecting the toluene bath in which the filter after suction filtration was immersed to ultrasonic treatment (As One, AZU-2M).
From the above, it is considered that the CNT enriched on the filter surface after suction-filtering the CNT dispersion is limited to the filter surface in a form that can be easily redispersed without a certain weak force accompanied by substantial binding or the like.
The results of examples 1 to 6 show that the CNT coating film can be formed on the substrate by the present invention using the CNT dispersions using various dispersion media.
Example 7
A CNT coating film, which is an example of a carbonaceous structure, was formed on the surface of various substrates other than the PET substrate using the CNT toluene dispersion prepared in example 6.
Fig. 4A to G show photographs of CNT films formed on the surfaces of various materials by the same method as in example 6. In addition to (a) the glass surface, the CNT coating film was also favorably formed on (B) the glass surface coated with a fluororesin (Cytop), (C) the polycycloolefin resin surface, and (D) the PTFE resin surface. The CNT coating film was also favorably formed on (E) a curved glass surface having a curvature or unevenness on the surface, (F) an aluminum foil surface, and (G) a rubber glove (nitrile rubber) surface. From the results of examples 6 and 7, it is understood that the CNT coating film and the like can be formed on the surface of the substrate having various materials and surface shapes by the method of the present invention.
Further, since the CNT coating film can be formed satisfactorily even on the surface of a PTFE resin made of the same material as that of a PTFE membrane filter (Millipore JGWP02500, 25mm Φ, pore size 0.2 μm) used as a porous membrane (fig. 4D), the CNT coating film formed by compressing and drying the filter and the substrate is particularly adhered to the substrate surface side due to the difference in effective contact area between the CNT coating film after drying and the filter/substrate, and it is considered that the reason is that the CNT coating film remains on the substrate side in contact with the CNT coating film in a larger effective area when the filter is peeled off.
Further, the CNT coating film can be favorably formed even on a surface having a curvature or unevenness (fig. 4E to G), and it is shown that by using a flexible porous film, the CNT coating film and the like can be formed by the surface tension of the dispersion liquid and the adhesion of the porous film to the fine portion of the base.
Example 8
After replacing the dispersion medium of the fine carbonaceous bodies used for forming the carbonaceous structures with another solvent or the like, a CNT coating film as an example of the carbonaceous structures is formed by the same method as described above.
To 5.0mL of distilled water in which 500mg of sodium dodecyl sulfate as a surfactant was dissolved, 0.50mg of SWCNT produced by the eDIPS method was added, and ultrasonic treatment was performed for 1 hour by an ultrasonic homogenizer to prepare an aqueous CNT dispersion. Then, 80. mu.L of this CNT aqueous dispersion was diluted with 2.0mL of water and 3.0mL of methanol to prepare a CNT dispersion using a water-methanol mixed solvent as a dispersion medium. The CNT dispersion was filtered by suction using a PTFE membrane filter (Millipore JGWP02500, 25 mm. phi., pore size 0.2 μm) until the dispersion on the filter disappeared immediately, thereby enriching the CNT on the filter. Subsequently, the process of supplying an appropriate amount of methanol to the filter and suction-filtering was repeated 3 times, and finally the suction-filtering was completed until the dispersion on the filter immediately disappeared.
Thereafter, the filter was taken out from the suction filter and immersed in a toluene bath, so that the filter sufficiently contained toluene. That is, the dispersion medium of the CNT aqueous dispersion was replaced with methanol on the filter in advance, and then the dispersion medium was replaced with toluene. The filter was quickly attached to the dried PET substrate, and was adhered to the surface of the PET substrate through the entire surface of the CNT-toluene dispersion. Thereafter, in the same manner as in example 6, toluene was evaporated off on a hot plate maintained at 70 ℃, and then the membrane filter was peeled off, thereby forming a black/translucent coating film on the surface of the PET substrate.
The PET substrate on which the CNT coating film was formed had an average transmittance of 71.3% and a surface resistance of 170 Ω/□, and a CNT coating film exhibiting characteristics comparable to those of the CNT coating film formed by the same SWCNT using the CNT aqueous dispersion (example 4) was formed.
Example 9
A CNT/graphene composite coating film, which is an example of a carbonaceous structure, was formed as a fine carbonaceous body using single-walled carbon nanotubes (SWCNTs) (ZEON ZEONANO SG101) produced by an ultrarapid growth method and graphene (ITEC ighurafen-as 180020C).
In order to disperse the CNTs and graphene in toluene, 0.45mg of the single-walled carbon nanotube (ZEON zeonono SG101) and 0.050mg of graphene (iGurafen-as 180020C) were added to 5.0mL of m-cresol (tokyo chemical corporation, > 98.0%), and ultrasonic treatment was performed for 2 hours using an ultrasonic homogenizer (bran son silicon ier 250), thereby dispersing the CNTs and graphene in m-cresol. The CNT dispersion was centrifuged (15000g, 1 hour) using a microfuge centrifuge (KUBOTA 3780), and the black supernatant was separated from the precipitate.
100. mu.L of the centrifuged supernatant was diluted with 5mL of toluene (Kanto chemical Special grade) to prepare a toluene dispersion. In the toluene dispersion, it was observed that CNTs and graphene as dispersoids were uniformly dispersed in toluene.
Then, a mixed coating of CNT and graphene was formed on a PET substrate and a glass substrate by, for example, enriching a mixture of CNT and graphene on a filter by suction filtration in the same manner as in example 6.
Fig. 5A shows a photograph of the mixed coating of CNTs and graphene formed into a PET substrate plate shape. As shown in fig. 5A, the formed CNT-graphene mixed film was black/translucent, and the average transmittance of the PET substrate to which the film was attached was 87.0% measured in the same manner as above. The surface resistance was 8.65 k.OMEGA./□.
Fig. 5B shows an SEM image of the mixed coating of CNTs and graphene formed into a glass substrate plate shape in the above description. It was confirmed that CNT and graphene were mixed to form a coating film.
Comparative example 1
A single-walled carbon nanotube (SWCNT) produced by the ultragrowth method (ZEON zeonono SG101) was dispersed in toluene (kanto chemical special grade) in the same manner as in example 6 to prepare a CNT-toluene dispersion, which was suction-filtered using a PTFE membrane filter (Millipore JGWP02500, 25mm Φ, pore size 0.2 μm), and the CNT was collected on the filter.
After that time, the user can use the device,the filter was removed from the suction filter and left in the air for a long time to be sufficiently dried. Upon drying, the filter changes from a translucent state to a grey opaque state. The dried filter was superposed on a PET substrate at a rate of 1kg/cm2The left and right pressures are uniformly applied to bond the filter and the PET substrate. After that, the filter was peeled off from the PET substrate, and as a result, almost all CNTs remained on the filter side, and no CNT coating film was formed on the PET substrate.
Comparative example 2
The CNT-enriched filter was sufficiently dried as in comparative example 1, immersed in a toluene bath to sufficiently absorb toluene, and then rapidly attached to the dried PET substrate. The filter was immersed in a toluene bath through a sufficiently dry filter, and rapidly wetted, and became translucent. At this time, no dispersion of CNTs into the toluene bath was observed, and it was considered that CNTs remained on the filter surface. Then, the wet filter was attached to the PET substrate, whereby the entire surface of the filter was in close contact with the surface of the PET substrate.
Thereafter, in the same manner as in example 6, toluene was evaporated and removed on a hot plate maintained at 70 ℃, and then the filter was peeled off, so that almost all CNTs remained on the filter side, and no CNT coating film was formed on the PET substrate.
When the toluene bath impregnated with the filter was subjected to ultrasonic treatment (As One, AZU-2M), it was observed that several minutes were required to cause almost all of the CNTs to be scattered from the filter, and a great difference was observed from the case where the drying step was not performed (example 6, etc.).
As is clear from the above, since physical adsorption or the like occurs between the CNTs and the filter as a result of direct contact between the CNTs and the filter being caused by drying the filter and removing the dispersion medium covering the surfaces of the CNTs, the CNTs are not easily re-dispersed in toluene even by immersion in a toluene bath, and therefore, unlike example 6, a CNT coating film cannot be formed on the surface of the PET substrate.
Industrial applicability
The method for forming a carbonaceous structure of the present invention can be suitably used for forming a carbonaceous structure containing various fine carbonaceous bodies.
Claims (8)
1. A method for forming a carbonaceous structure in which a carbonaceous structure is formed on a surface of a base, the method comprising:
a laminate forming step of forming a laminate in which a fine carbonaceous body dispersion liquid containing a fine carbonaceous body and a dispersion medium is filled in at least a part of a space between a porous film capable of holding the dispersion medium and a substrate; and
a dispersion medium removing step of taking out at least a part of the dispersion medium to the outside of the laminate through the porous membrane and/or the matrix.
2. The method of forming a carbonaceous structure according to claim 1, wherein the laminate is formed by stacking the porous membrane, which holds the fine carbonaceous body dispersion by suction filtration, on a substrate.
3. The method of forming a carbonaceous structure according to claim 1, wherein the laminate is formed by further immersing the porous membrane, which holds the fine carbonaceous body dispersion liquid after suction filtration of the fine carbonaceous body dispersion liquid, in a solvent and then overlapping the porous membrane with a matrix.
4. The method of forming a carbonaceous structure according to claim 2 or 3, wherein a dispersion medium contained in the fine carbonaceous body dispersion liquid is replaced with another dispersion medium in the suction filtration.
5. The method of forming a carbonaceous structure according to any one of claims 1 to 4, wherein the dispersion medium removal step is performed by evaporating the dispersion medium through the pores of the porous film.
6. The method of forming a carbonaceous structure according to any one of claims 1 to 5, further comprising a step of removing the porous film from the formed carbonaceous structure.
7. The method of forming a carbonaceous structure according to claim 6, wherein the step of removing the porous film is performed by peeling the porous film from the carbonaceous structure.
8. A substrate having a carbonaceous structure comprising a fine carbon body, wherein the carbonaceous structure is formed in a process of taking out at least a part of a dispersion medium out of a laminate, which is obtained by filling at least a part of a space between a porous film capable of holding the dispersion medium and the substrate, from a fine carbon body dispersion liquid comprising the fine carbon body and the dispersion medium, through the porous film and/or the substrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-194828 | 2019-10-26 | ||
| JP2019194828A JP7376077B2 (en) | 2019-10-26 | 2019-10-26 | Method for forming a carbonaceous structure and substrate having a carbonaceous structure |
| PCT/JP2020/039920 WO2021079990A1 (en) | 2019-10-26 | 2020-10-23 | Carbonaceous structure forming method and substrate having carbonaceous structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114599605A true CN114599605A (en) | 2022-06-07 |
Family
ID=75619322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080074703.2A Pending CN114599605A (en) | 2019-10-26 | 2020-10-23 | Method for forming carbonaceous structure and substrate having carbonaceous structure |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20240102158A1 (en) |
| EP (1) | EP4049969A1 (en) |
| JP (1) | JP7376077B2 (en) |
| KR (1) | KR20220087505A (en) |
| CN (1) | CN114599605A (en) |
| WO (1) | WO2021079990A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011009131A (en) * | 2009-06-29 | 2011-01-13 | Jfe Engineering Corp | Method for manufacturing electron source electrode |
| US20120076974A1 (en) * | 2010-09-29 | 2012-03-29 | Teledyne Scientific & Imaging, Llc | Vertically aligned carbon nanotube arrays from liquid dispersions |
| CN107001046A (en) * | 2014-12-25 | 2017-08-01 | 日本瑞翁株式会社 | Carbon nano-tube film and its manufacture method |
| CN107406256A (en) * | 2015-03-31 | 2017-11-28 | 日本瑞翁株式会社 | Carbon film and its manufacture method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006008473A (en) | 2004-06-29 | 2006-01-12 | Mitsubishi Gas Chem Co Inc | Method for manufacturing cylindrical aggregate obtained by patterning oriented carbon nanotube and field emission type cold cathode |
| US20060188721A1 (en) | 2005-02-22 | 2006-08-24 | Eastman Kodak Company | Adhesive transfer method of carbon nanotube layer |
| JP2008273785A (en) | 2007-04-27 | 2008-11-13 | Meijo Nano Carbon:Kk | Method for production of substrate with carbon nanotube |
| JP6044823B2 (en) | 2012-08-24 | 2016-12-14 | 国立大学法人 東京大学 | Transparent electrode, method for producing conductive transparent thin film, and conductive transparent thin film |
-
2019
- 2019-10-26 JP JP2019194828A patent/JP7376077B2/en active Active
-
2020
- 2020-10-23 EP EP20879303.4A patent/EP4049969A1/en active Pending
- 2020-10-23 WO PCT/JP2020/039920 patent/WO2021079990A1/en active Application Filing
- 2020-10-23 US US17/768,910 patent/US20240102158A1/en active Pending
- 2020-10-23 KR KR1020227017071A patent/KR20220087505A/en active Search and Examination
- 2020-10-23 CN CN202080074703.2A patent/CN114599605A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011009131A (en) * | 2009-06-29 | 2011-01-13 | Jfe Engineering Corp | Method for manufacturing electron source electrode |
| US20120076974A1 (en) * | 2010-09-29 | 2012-03-29 | Teledyne Scientific & Imaging, Llc | Vertically aligned carbon nanotube arrays from liquid dispersions |
| CN107001046A (en) * | 2014-12-25 | 2017-08-01 | 日本瑞翁株式会社 | Carbon nano-tube film and its manufacture method |
| CN107406256A (en) * | 2015-03-31 | 2017-11-28 | 日本瑞翁株式会社 | Carbon film and its manufacture method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20220087505A (en) | 2022-06-24 |
| US20240102158A1 (en) | 2024-03-28 |
| EP4049969A1 (en) | 2022-08-31 |
| JP7376077B2 (en) | 2023-11-08 |
| WO2021079990A1 (en) | 2021-04-29 |
| JP2021066642A (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lacey et al. | Extrusion‐based 3D printing of hierarchically porous advanced battery electrodes | |
| JP5858266B2 (en) | Method for producing carbon nanotube composite | |
| US9284193B2 (en) | Method for preparing graphene oxide films and fibers | |
| US20230253350A1 (en) | Integration and bonding of micro-devices into system substrate | |
| US8445889B2 (en) | Method of patterning of nanostructures | |
| Li et al. | Transparent and self-supporting graphene films with wrinkled-graphene-wall-assembled opening polyhedron building blocks for high performance flexible/transparent supercapacitors | |
| JP2018535130A (en) | Multi-layer composite comprising an adhesive and one or more nanofiber sheets | |
| KR101073853B1 (en) | Fabrication method of gauze like film made up of nano-structured molecules on substrate and substrate with gauze like nano-structured molecules film thereby | |
| US9656862B2 (en) | High surface area nano-structured graphene composites and capacitive devices incorporating the same | |
| Krane | Preparation of graphene | |
| JP2008103164A (en) | Composite material of carbon and water-repellent material | |
| JP4093439B2 (en) | Method for producing electrode for polymer electrolyte fuel cell | |
| JP2015526382A (en) | Graphene sheet and manufacturing method thereof | |
| Sugioka et al. | Single-step preparation of two-dimensionally organized gold particles via ionic liquid/metal sputter deposition | |
| KR101838637B1 (en) | Thin film of nanoparticle-graphene oxide composite and method for producing the same | |
| CN110240155B (en) | Interface assembly large-area uniform carbon material film, preparation method and application thereof | |
| CN114599605A (en) | Method for forming carbonaceous structure and substrate having carbonaceous structure | |
| JPWO2006103967A1 (en) | Polarized electrode, capacitor using the same, and method for producing polarizable electrode | |
| KR100977541B1 (en) | Porous Carbon Nanotube Film and the Fabrication Method Thereof | |
| EP2842910A1 (en) | Method of preparing graphene paper | |
| D'Arcy et al. | Aligned carbon nanotube, graphene and graphite oxide thin films via substrate-directed rapid interfacial deposition | |
| JP7054164B2 (en) | Capacitive energy storage device and method of making the device | |
| KR20210071176A (en) | Manufacturing method of mxene film | |
| JP2022159276A (en) | Conductive film transfer sheet and manufacturing method thereof, conductive object and manufacturing method thereof, and conductive film | |
| JP2022159276A5 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |